EP0305837B1 - Ester d'acide thionophosphonique - Google Patents

Ester d'acide thionophosphonique Download PDF

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Publication number
EP0305837B1
EP0305837B1 EP88113590A EP88113590A EP0305837B1 EP 0305837 B1 EP0305837 B1 EP 0305837B1 EP 88113590 A EP88113590 A EP 88113590A EP 88113590 A EP88113590 A EP 88113590A EP 0305837 B1 EP0305837 B1 EP 0305837B1
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EP
European Patent Office
Prior art keywords
methyl
alkyl
spp
formula
pyrimidin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP88113590A
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German (de)
English (en)
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EP0305837A3 (en
EP0305837A2 (fr
Inventor
Fritz Dr. Maurer
Bernhard Dr. Homeyer
Wolfgang Dr. Behrenz
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Bayer AG
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Bayer AG
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Priority to AT88113590T priority Critical patent/ATE73812T1/de
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Publication of EP0305837A3 publication Critical patent/EP0305837A3/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/24—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing heterocyclic radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
    • C07F9/6509—Six-membered rings
    • C07F9/6512—Six-membered rings having the nitrogen atoms in positions 1 and 3

Definitions

  • the invention relates to new O- (6-methyl-2-alkyl-pyrimidin-4-yl) -O-alkyl-thionoalkanephosphonic acid diesters, a process for their preparation and their use as pesticides, preferably as insecticides.
  • O- (2,6-dialkyl-pyrimidin-4-yl) -O-alkyl-thionoalkanephosphonic acid diesters such as.
  • B. O- (2-methyl-6-tert-butyl-pyrimidin-4-yl) -O-ethyl-thionomethanephosphonic acid diester and O- (2,6-dimethyl-pyrimidin-4-yl) -O-methyl- thiono-ethanephosphonic acid diesters are suitable for combating insects (cf. DE-OS 11 40 580 and DE-OS 26 39 433).
  • the insecticidal activity of these known compounds is not always satisfactory, in particular when the application rates are low or when the active substance is concentrated, and in terms of the duration of action.
  • the new compounds of formula (I) in particular show an outstanding activity against Orthoptera, such as. B. Blattella germanica and Coleoptera, such as. B. Sitophilus granarius. Also against ground insects (i.e. insects that occur in or on the ground or near the ground), such as. B. Phorbia antiqua maggots and Diabrotica balteata larvae, the active compounds according to the invention show outstanding activity.
  • Orthoptera such as. B. Blattella germanica and Coleoptera, such as. B. Sitophilus granarius.
  • ground insects i.e. insects that occur in or on the ground or near the ground
  • the O- (6-methyl-2-alkyl-pyrimidin-4-yl) -O-alkyl-thionoalkanephosphonic acid diesters of the formula (I) according to the invention show considerably stronger insecticidal activity than the above-mentioned O- (2,6-dialkyl) -pyrimidin-4-yl) -O-alkyl-thionoalkanephosphonic acid diesters.
  • the substances according to the invention thus represent a valuable addition to the technology.
  • Formula (II) defines the 6-methyl-2-alkyl-4-hydroxy-pyrimidines to be used as starting materials.
  • the alkali metal or alkaline earth metal salts are preferably the sodium, potassium or calcium salts.
  • Examples include 6-methyl-2-tert-butyl-4-hydroxy-pyrimidine and 6-methyl-2-isopropyl-4-hydroxy-pyrimidine.
  • 6-methyl-2-alkyl-4-hydroxy-pyrimidines of the formula (II) are known (cf. DE-OS 20 65 698 or J. Chem. Soc. (London) 1963 , p. 5652).
  • the thionoalkanephosphonic acid chloride alkyl esters of the formula (III) to be used as starting material are already known (cf. DE-OS 10 78 124, GB-PS 1 450 284 and DE-OS 29 20 172).
  • the process according to the invention for the preparation of the new compounds of the formula (I) is preferably carried out using diluents and acid acceptors.
  • inert organic solvents can be used as diluents.
  • These preferably include aliphatic and aromatic, optionally halogenated hydrocarbons such as pentane, hexane, heptane, cyclohexane, petroleum ether, gasoline, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers such as diethyl and Dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl, methyl isopropyl and methyl isobutyl ketone, esters such as methyl acetate and ethyl acetate, nitriles such as e.g.
  • Acid acceptors which can be used in the process according to the invention are all acid binders which can customarily be used for such reactions.
  • Alkali metal hydroxides such as, for. B. sodium and potassium hydroxide, alkaline earth metal hydroxides such. B.
  • alkali carbonates and alcoholates such as sodium and potassium carbonate, sodium and potassium tert-butoxide, also aliphatic, aromatic or heterocyclic amines, for example triethylamine, trimethylamine, dimethylaniline, dimethylbenzylamine, pyridine, 1,5-diazabicyclo- [4 , 3,0] non-5-ene (DBN), 1,8-diazabicyclo- [5,4,0] -undec-7-ene (DBU) and 1,4-diazabicyclo- [2,2,2 ] octane (DABCO).
  • DBN 1,5-diazabicyclo- [4 , 3,0] non-5-ene
  • DBU 1,8-diazabicyclo- [5,4,0] -undec-7-ene
  • DABCO 1,4-diazabicyclo- [2,2,2 ] octane
  • reaction temperatures can be varied within a wide range in the process according to the invention. In general, temperatures between 0 ° C and 100 ° C, preferably at temperatures between 10 ° C and 80 ° C.
  • the process according to the invention is generally carried out under normal pressure. However, it is also possible to work under increased or reduced pressure.
  • the starting materials of the formulas (II) and (III) are generally used in approximately equimolar amounts. However, an excess of one or the other component up to about 10% is possible without any problems.
  • reaction components are generally combined in one of the solvents given above and stirred for several hours, the temperature being kept within the scope given above.
  • the mixture is concentrated, the residue in a water-immiscible solvent, such as. As toluene, added, washed with water and with a conventional drying agent such as. B. sodium sulfate, dried. After filtration, the solvent is distilled off from the filtrate in a water jet vacuum.
  • a water-immiscible solvent such as. As toluene
  • a conventional drying agent such as. B. sodium sulfate
  • the new compounds are obtained in the form of oils, some of which cannot be distilled without decomposing, but by so-called “distillation", i.e. H. can be freed from the last volatile constituents by prolonged heating under reduced pressure to moderately elevated temperatures and can be cleaned in this way.
  • the refractive index is used to characterize them.
  • the active compounds are suitable for controlling animal pests, preferably arthropods and nematodes, in particular insects and arachnids, which are in the Agriculture, forestry, storage and material protection, and in the hygiene sector. They are effective against normally sensitive and resistant species as well as against all or individual stages of development.
  • animal pests preferably arthropods and nematodes, in particular insects and arachnids, which are in the Agriculture, forestry, storage and material protection, and in the hygiene sector. They are effective against normally sensitive and resistant species as well as against all or individual stages of development.
  • the pests mentioned above include:
  • Isopoda for example Oniscus asellus, Armadillidium vulgare, Porcellio scaber.
  • Diplopoda for example, Blaniulus guttulatus.
  • Chilopoda for example, Geophilus carpophagus and Scutigera spec.
  • Symphyla for example, Scutigerella immaculata.
  • Thysanura for example Lepisma saccharina.
  • Collembola for example Onychiurus armatus.
  • Orthoptera for example Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.
  • Dermaptera for example, Forficula auricularia.
  • Isoptera for example Reticulitermes spp ..
  • Anoplura for example Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp.
  • Mallophaga for example Trichodectes spp., Damalinea spp.
  • Thysanoptera for example Hercinothrips femoralis, Thrips tabaci.
  • Heteroptera for example Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.
  • From the order of the Homoptera for example, Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Phyphodosumas, Myzus sppas spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp.
  • Psylla spp From the order of the Lepidoptera, for example Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp.
  • Siphonaptera for example Xenopsylla cheopis, Ceratophyllus spp ..
  • Arachnida for example Scorpio maurus, Latrodectus mactans.
  • Acarina for example Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp ..
  • the plant parasitic nematodes include Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp.
  • the active compounds according to the invention are notable for excellent insecticidal activity, in particular in the control of Orthoptera species, such as. B. Blattella germanica and Coleoptera species, such as. B. Sitophilus granarius.
  • the active compounds according to the invention can also be used very effectively to control soil insects, such as, for. B. Phorbia antiqua maggots and Diabrotica balteata larvae can be used.
  • Some of the active compounds according to the invention also show leaf-insecticidal activity.
  • the active substances can be converted into customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, active substance-impregnated natural and synthetic substances, very fine encapsulations in polymeric substances and in coating compositions for seeds, furthermore in formulations with fuel sets, such as smoking cartridges, cans, spirals and the like, as well as ULV cold and warm mist formulations.
  • customary formulations such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, active substance-impregnated natural and synthetic substances, very fine encapsulations in polymeric substances and in coating compositions for seeds, furthermore in formulations with fuel sets, such as smoking cartridges, cans, spirals and the like, as well as ULV cold and warm mist formulations.
  • formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents.
  • extenders that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents.
  • surface-active agents that is to say emulsifiers and / or dispersants and / or foam-generating agents.
  • organic solvents can, for example, also be used as auxiliary solvents.
  • liquid solvents aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water; with liquefied gaseous Extenders or carriers are those liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide; Solid carrier materials are suitable: for example natural
  • Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and also natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations.
  • Other additives can be mineral and vegetable oils.
  • Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.
  • the formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
  • the active compounds can be present in their commercially available formulations and in the use forms prepared from these formulations in a mixture with other active compounds, such as insecticides, attractants, sterilants, acaricides, nematicides, fungicides, growth-regulating substances or herbicides.
  • Insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms, etc.
  • the active compounds can also be present in their commercially available formulations and in the use forms prepared from these formulations in a mixture with synergists.
  • Synergists are compounds by which the action of the active ingredients is increased without the added synergist itself having to be active.
  • the active substance content of the use forms prepared from the commercially available formulations can vary within wide ranges.
  • the active substance concentration of the application forms can be from 0.0000001 to 95% by weight of active compound, preferably between 0.0001 and 1% by weight.
  • the application takes place in a customary manner adapted to the application forms.
  • the active ingredients When used against hygiene pests and pests of stored products, the active ingredients are distinguished by an excellent residual action on wood and clay and by a good stability to alkali on limed substrates.
  • Test animals Blatella germanica Number of animals: 25 Solvent: acetone
  • active ingredient preparation is intimately mixed with the soil.
  • the efficiency is 100% when all test insects have been killed, it is 0% when as many test insects are still alive as in the untreated control.
  • the compounds of Examples (1) and (2) showed a degree of killing of 100% at an exemplary concentration of 5 ppm, while at the same concentration the comparison compound (A) gave no killing (0%).
  • active ingredient preparation is intimately mixed with the soil.
  • 6 pre-germinated corn kernels are placed in each pot. After 2 days, the appropriate test insects are placed in the treated soil. After a further 7 days, the effectiveness of the active ingredient is determined by counting the dead and live test insects in%.
  • the efficiency is 100% when all test insects have been killed, it is 0% when as many test insects are still alive as in the untreated control.
  • the compounds of Examples (1) and (2) showed a degree of killing of 100% at an exemplary concentration of 5 ppm, while at the same concentration the comparison compound (A) gave no killing (0%).

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Molecular Biology (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Saccharide Compounds (AREA)
  • Medicinal Preparation (AREA)

Claims (8)

  1. Diesters thionoalcanephosphonates de O-(6-méthyl-2-alkyl-pyrimidine-4-yle)-O-alkyle de formule générale (I)
    Figure imgb0021
     dans laquelle
    R   signifie méthyle ou éthyle,
    R¹   signifie méthyle ou éthyle et
    R²   signifie isopropyle ou tert-butyle.
  2. Composé de formule
    Figure imgb0022
  3. Composé de formule
    Figure imgb0023
  4. Procédé pour la fabrication de diesters thionoalcanephosphonates de O-(6-méthyl-2-alkyl-pyrimidine-4-yle)-O-alkyle de formule générale (I)
    Figure imgb0024
     dans laquelle
    R   signifie méthyle ou éthyle,
    R¹   signifie méthyle ou éthyle et
    R²   signifie isopropyle ou tert-butyle,
    caractérisé en ce que l'on fait réagir des 6-méthyl-2-alkyl-4-hydroxy-pyrimidines de formule générale (II)
    Figure imgb0025
     dans laquelle
    R²   possède la signification décrite ci-dessus ou représente ses sels de métaux alcalins, de métaux alcalino-terreux ou d'ammonium,
    avec des chlorures de thionoalcanephosphonates d'alkyle de formule (III)
    Figure imgb0026
     dans laquelle
    R et R¹ possèdent les significations décrites ci-dessus, éventuellement en présence d'un accepteur d'acide et éventuellement en présence d'un diluant.
  5. Utilisation des diesters thionoalcanephosphonates de O-(6-méthyl-2-alkyl-pyrimidine-4-yle)-O-alkyle de formule (I) selon les revendications 1 ou 4 comme arthropodicides.
  6. Agent insecticide et acaricide, caractérisé en ce qu'il contient des diesters thionoalcanephosphonates de O-(6-méthyl-2-alkyl-pyrimidine-4-yle)-O-alkyle de formule (I) selon les revendications 1 ou 4.
  7. Procédé pour la lutte contre les arthropodes nuisibles, caractérisé en ce qu'on traite ces derniers ou leur habitat avec des diesters thionoalcanephosphonates de O-(6-méthyl-2-alkyl-pyrimidine-4-yle)-O-alkyle de formule (I) selon les revendications 1 ou 4.
  8. Procédé pour la fabrication d'agents arthropodicides, caractérisé en ce qu'on mélange des diesters thionoalcanephosphonates de O-(6-méthyl-2-alkyl-pyrimidine-4-yle)-O-alkyle de formule (I) selon les revendications 1 ou 4 avec des agents d'allongement ou de dilution.
EP88113590A 1987-09-02 1988-08-22 Ester d'acide thionophosphonique Expired - Lifetime EP0305837B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88113590T ATE73812T1 (de) 1987-09-02 1988-08-22 Thionophosphonsaeureester.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19873729263 DE3729263A1 (de) 1987-09-02 1987-09-02 Thionophosphonsaeureester
DE3729263 1987-09-02

Publications (3)

Publication Number Publication Date
EP0305837A2 EP0305837A2 (fr) 1989-03-08
EP0305837A3 EP0305837A3 (en) 1989-11-15
EP0305837B1 true EP0305837B1 (fr) 1992-03-18

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ID=6335025

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88113590A Expired - Lifetime EP0305837B1 (fr) 1987-09-02 1988-08-22 Ester d'acide thionophosphonique

Country Status (14)

Country Link
US (1) US4940698A (fr)
EP (1) EP0305837B1 (fr)
JP (1) JPS6471891A (fr)
KR (1) KR890005135A (fr)
AT (1) ATE73812T1 (fr)
AU (1) AU2169088A (fr)
BR (1) BR8804486A (fr)
DE (2) DE3729263A1 (fr)
DK (1) DK484988A (fr)
ES (1) ES2034070T3 (fr)
HU (1) HUT49621A (fr)
IL (1) IL87599A0 (fr)
PT (1) PT88320B (fr)
ZA (1) ZA886504B (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4015715A1 (de) * 1990-05-16 1991-11-21 Bayer Ag Neuartige oligophosphate mit antiviraler wirkung
AU7595701A (en) * 2000-07-17 2002-01-30 Harvard College Surfaces that resist the adsorption of biological species

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ZA15258B (fr) * 1951-04-20 1900-01-01
BE589122A (fr) * 1959-03-28 1900-01-01
DE2639433A1 (de) * 1976-09-02 1978-03-09 Bayer Ag Pyrimidinyl(thiono)(thiol)-phosphor(phosphon)-saeureester, verfahren zu ihrer herstellung und ihre verwendung als insektizide und akarizide
DE2853450A1 (de) * 1978-12-11 1980-06-19 Basf Ag Thionophosphonsaeureester
DE3445465A1 (de) * 1984-12-13 1986-06-19 Bayer Ag, 5090 Leverkusen Pyrimidinyl-thionophosphorsaeureester

Also Published As

Publication number Publication date
DK484988A (da) 1989-03-03
ZA886504B (en) 2008-05-30
ATE73812T1 (de) 1992-04-15
US4940698A (en) 1990-07-10
HUT49621A (en) 1989-10-30
PT88320B (pt) 1992-10-30
KR890005135A (ko) 1989-05-13
IL87599A0 (en) 1989-01-31
DE3729263A1 (de) 1989-03-23
BR8804486A (pt) 1989-03-28
ES2034070T3 (es) 1993-04-01
EP0305837A3 (en) 1989-11-15
EP0305837A2 (fr) 1989-03-08
DK484988D0 (da) 1988-08-31
AU2169088A (en) 1989-03-02
DE3869279D1 (en) 1992-04-23
PT88320A (pt) 1989-07-31
JPS6471891A (en) 1989-03-16

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